This dissertation describes work completed in several areas of ongoing research in the Vanderwal Lab. Chapter 1 describes the family of natural products known as the abietane diterpenoids, the structural anomaly plebeianiol A, and our synthetic endeavor to elucidate the authentic structure of this natural product. Chapter 2 describes the development of a new radical/polar crossover annulation method using metal-hydride hydrogen atom transfer (MHAT) catalysis. Finally, Chapter 3 details our investigation into a synthetic route towards the sesterterpenoid natural product, asperterpenoid A.